JP2008522867A - Patterning stamp, method for manufacturing the stamp, and method for manufacturing an object using the stamp - Google Patents

Abstract

A stamp for patterning onto a receiving surface (103) of an object (101) according to a defined pattern (P) comprises a stamping surface (21) of a resilient diaphragm (20). The stamping surface (21) is planar at rest. The pattern (P) is reproduced on the stamping surface (21) and the diaphragm (20) is affixed to a rigid body (13) along a peripheral edge, so that a middle part of the diaphragm (20) can move along a direction perpendicular to the stamping surface (21). The diaphragm (20) is more flexible near the peripheral edge than in the middle part. Then, the pattern (P) printed on a pseudo-spherical receiving surface (103) using the stamp exhibits few distortion.

Description

  The present invention relates to a stamp for patterning a receiving surface and a method for manufacturing the stamp. The invention also relates to a method for producing an object, which comprises a printing process carried out by using a stamp according to the invention.

  Soft lithography and in particular microcontact printing are known methods for replicating patterns quickly and at low cost, the replication accuracy of which can be higher than 0.50 μm (micrometers). The method is to press the stamp surface of the stamp soaked with ink against the receiving surface so that the ink is transferred from the stamp surface to the receiving surface according to the pattern.

  Patent Document 1 and Patent Document 2 disclose improvements of a microcontact printing method that achieves large pattern printing. However, these improved methods cannot be used for printing on spheres or pseudospheres. Within the scope of the present invention, a pseudo-spherical surface means a continuous plane (that is, no step or gap) and is a convex surface or a concave surface. The spherical surface is a special case where the curvature radii of the surfaces along two mutually orthogonal directions are equal. Therefore, the expression “pseudo-spherical surface” used in this specification includes the case of a spherical surface.

  Non-Patent Document 1 reports on microcontact printing on a non-planar surface. However, the method described in that document is not suitable for a receiving surface having a pseudo-spherical shape.

Finally, Patent Document 3 discloses a stamp having a convex stamp surface. The stamp surface gradually flattens with respect to the receiving side, while the periphery of the stamp surface is held fixed. Such asymptotic contact between the stamp surface and the receiver avoids bubble trapping, and a pseudospherical receiver surface is used for such contact. However, this method produces a distorted pattern print because the strain distribution generated on the stamp surface is not uniform during application to the receiving surface.
US Pat. No. 5,937,758 US Patent Application Publication No. 2004/0011231 US Pat. No. 5,669,303 Y. Xia and G.G. M.M. Whitesides, “Soft lithography” Angew. Chem. Int. Ed. 1998, 37, 550-575. “Light-coupling masks for lensless, sub-wavelength optical lithography” (Applied Physics Letters, Vol. 72, page 2379 1998). American Chemical Society, “Positive Microcontact Printing”, 2002, 124, 3834 "Patterned Electrodeposition of Copper by Microcontact Printing Palladium (II) complexes on Titanium-covered surfaces", Langmuir 2000, Vol. 16, 6367.

  Therefore, an object of the present invention is to provide a stamp for printing a pattern used on a receiving side having a pseudo-spherical shape.

  Accordingly, the present invention provides a stamp that is patterned on the receiving side according to a specified pattern, the stamp comprising an elastic diaphragm stamp surface on which the pattern is replicated. The stamp surface can be flat at rest or can have a shape that fits the particular substrate to be printed. The diaphragm is attached to the rigid body along the periphery of the diaphragm so that the point at the middle of the diaphragm is movable relative to the rigid body along a direction perpendicular to the stamp surface. Further, the diaphragm is more elastic in the vicinity of the peripheral portion than in the intermediate portion. In the context of the present invention, “movement along a direction perpendicular to the stamp surface”, ie the movement of the diaphragm along an axis parallel to the normal passing through the center point of the stamp surface is an angle of ± 20 °. It is understood as having a tolerance.

  The elastic diaphragm forms the stamp surface of the stamp according to the invention, so that when the stamp surface is pressed against the receiving surface, the shape of the stamp surface can change to match the shape of the receiving side. The stamp can be used to print a pattern on the receiving surface having a pseudo-spherical shape.

  Such a change in the shape of the stamp surface of the stamp can induce pattern distortion, especially for a receiving surface with a small radius of curvature. However, such distortion is limited by providing a more elastic diaphragm periphery. In practice, the curvature of the diaphragm is mainly located at the most elastic peripheral edge of the diaphragm, so that the pattern in the central part of the diaphragm is only slightly distorted while pressing the stamp surface against the receiving side. Therefore, the pattern can be printed with high accuracy on the receiving surface having a pseudo-spherical shape.

  In accordance with a preferred embodiment of the present invention, higher elasticity of the diaphragm near the periphery is obtained by reducing the thickness of the diaphragm in this region. Thus, the diaphragm is thinner in the ring-shaped part near the peripheral part than in the intermediate part surrounded by the ring-shaped part. This method of varying the elasticity of the diaphragm between the periphery and the middle is simple and can be easily implemented during the manufacture of the stamp. Furthermore, once the change in diaphragm elasticity between the peripheral and intermediate portions is determined once during the manufacture of the stamp, it no longer needs to be controlled during printing on the receiving side.

  According to another embodiment of the invention, the diaphragm comprises a number of elastic layers stacked along a direction orthogonal to the stamp surface, the stamp surface including the most rigid elastic layer of the diaphragm layers. Thus, the pattern is less distorted when printed on the receiving surface having a pseudo-spherical shape. The two-layer structure of the diaphragm is particularly suitable for high resolution printing.

  The above-described stamp fits a receiving surface that is convex. In this case, when the stamp surface is pressed against the receiving surface, contact between the diaphragm and the receiving side begins at the middle of the stamp and then extends radially. The inventors have found that this action reduces the distortion of pattern printing on the receiving side.

  The stamp according to the invention can also be adapted to a concave receiving surface. For this purpose, the stamp also has a sealed housing bounded by a diaphragm, and a means by which the pressure within the housing can be varied to control the concave or convex surface of the stamp surface by pressure. Further prepare. It is then possible to set the shape of the stamp surface according to the shape of the receiving surface before printing. Such an initial setting of the shape of the stamp surface is useful for concave receiver surfaces, but it can also improve pattern printing accuracy for convex receiver surfaces. The pressure in the housing is high when printing on a concave surface, so that the initial contact between the stamp surface and the receiving surface occurs at approximately the central portion of the stamp. In the case of a convex receiving surface, the pressure in the housing can be increased, but preferably the pressure is reduced to reduce diaphragm distortion during application to the receiving surface. As a result, pattern printing distortion is reduced.

  The present invention also provides a method of manufacturing such a stamp, providing a pattern at the bottom of the mold that is replicated on the mold bottom plane, such that the inner bottom edge of the mold side portion surrounds the pattern. , A step of disposing the mold side portion at the bottom of the mold, wherein the mold side portion includes a lower mold side portion and an upper mold side portion, and the individual internal bores are arranged in a line, A mold bottom overlapped to form an elastomer diaphragm having a thickness greater than the height of the bottom side bore, with one bore made larger in cross-section than the other mold side portion bore; Injecting at least one elastomer precursor into a mold having a mold side portion; Along the periphery of the diaphragm corresponding to the largest bore of the mold side parts and upper mold side parts, and a step of fixing the diaphragm to the rigid part.

  Such a stamp manufacturing method is easy and inexpensive. The reason is that it does not require any complicated technical means. In addition, known techniques such as silicon wafer lithography are also used to replicate the pattern on the mold bottom. This is because the stamp surface is designed to be flat in a stationary state.

  Preferably, the upper mold side portion has a larger bore than the lower mold side portion.

  For greater ease of handling, the lower mold side part and the upper mold side part are separate parts, and means are provided for joining the lower mold side part and the upper mold side part in a row.

  In accordance with a preferred implementation of the stamp manufacturing method, the method further includes the step of applying an elastomer adhesion promoter to the inner surface of the mold side portion having the largest bore before injecting the elastomer precursor.

  Also, the mold side portion having the largest bore is a part of the rigid portion of the stamp. Therefore, if the diaphragm is formed directly attached to the rigid body, the manufacture of the stamp is greatly simplified. This avoids a separate manufacturing process that secures the diaphragm to the rigid body. Note that such a fixing step can induce distortion of the pattern due to the permanent curvature of the diaphragm.

  Advantageously, the mold side part with the largest bore comprises an inner groove in which an adhesion promoter is applied. Therefore, the application of the adhesion promoter is more easily performed so that it is uniformly achieved. As a result, the diaphragm is substantially uniformly attached to the rigid body portion, and pattern printing distortion is reduced.

  The present invention also provides a method of manufacturing an object having a pattern printed on a receiving surface having a pseudo-spherical shape of the object, the step of applying ink to the stamp surface of the above-mentioned stamp, and the object Pressing the stamp surface of the stamp against the receiving surface, removing the stamp from the object, and processing the receiving surface by wet etching or chemical plating.

  In accordance with this preferred embodiment of the present invention, the ink is transferred from the stamp to the substrate during printing. The substrate is coated with a receiver layer that forms a receiver surface. The ink is made of a molecular material that protects the receiving layer against, for example, wet etching. The present invention is also useful for performing near-field optical lithography by using a stamp as a contact phase mask. An example is described in Non-Patent Document 2. In this case, the elastic diaphragm of the stamp is made of a siloxane-type elastomer material that transmits UV light. According to another embodiment, the present invention also provides a method for producing an object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101), and having a concave surface. A step of laminating a light-absorbing layer on the stamp surface, a step of applying a photoresist to the receiving surface, and pressing the stamp surface (21) against the receiving surface (103) of the object as a light coupling mask And using the above-described stamp, including the steps of exposing the stamp to UV light, removing the stamp from the object, and developing the photoresist. Such a manufacturing method is quick and inexpensive. In fact, the entire pattern is printed on the object by pressing in a single motion, ie a simple movement of the stamp relative to the object. They can also be implemented by using a very simple motion control device.

  Furthermore, the same stamp can be used for various radii of curvature on the receiving surface of the object. The receiving surface may have a radius of curvature greater than 55 mm (millimeters). That is, the same stamp can be used for objects having individual receiver surfaces of different shapes.

  Such a manufacturing method of the object is suitable for patterns having submicron fineness due to the high accuracy of the printing obtained.

  If the stamp comprises a sealed housing and pressure adjusting means to make the stamp surface convex or concave, the method of manufacturing the object further presses the stamp surface of the stamp against the receiving surface of the object Before the stamp surface and the receiver surface have complementary shapes, and pressing the stamp surface against the receiver surface is initiated by contacting the middle portion of the stamp surface. Adjusting the pressure. In the present invention, the “complementary shape” is a convex receiving surface, and the curvature radius of the stamp surface is equal to or exceeds the curvature radius of the receiving surface, and the concave receiving surface. This means that the radius of curvature of the stamp surface is equal to or less than the radius of curvature of the receiving surface.

  When using such an improvement of the printing process, the same stamp can be used for receiving surfaces with different curvatures, including concave receiving surfaces and convex receiving surfaces. Accordingly, the variety of shapes of objects that match the same stamp increases.

  A useful application of the invention relates to the production of optical lenses having a pattern. In fact, optical lenses often have a quasi-spherical surface to modify the spread of light that strikes the lens. The lens may also be an ophthalmic lens, ie, any lens designed for eyeglasses, with or without optical correction and with or without color. The ophthalmic lens may be afocal, single focus, bifocal, trifocal or progressive multifocal.

  These and other aspects of the invention will become apparent from the non-limiting embodiments described herein with reference to the following drawings.

  In these drawings, the same reference numerals indicate the same elements or elements having similar functions. Further, for clarity, the element sizes shown do not correspond to the actual element sizes.

  The stamp manufacturing process will be described in detail with reference to FIG. A mold 100 for manufacturing a stamp is composed of four parts, namely a base 10, a master 11, a lower mold side part 12, and an upper mold side part 13, and is designed to be stacked with precise alignment. Base 10, lower mold side portion 12, and upper mold side portion 13 are aluminum, polyoxymethylene, or formally stable and sufficient surface properties to promote or avoid adhesion to elastomer Any other material having The base 10 together with the master 11 disposed in the recess of the base forms the mold bottom 1 of the mold 100. The lower mold side portion 12 and the upper mold side portion 13 form the mold side portion 2 of the mold 100. The base 10, the master 11, the lower mold side portion 12, and the upper mold side portion 13 are provided by using a general assembling means, and are configured to obtain a mold 100 assembled with an alignment accuracy of up to 10 μm. The

  Advantageously, the master 11 consists of a silicon wafer commonly used in microelectronics. For example, the wafer is about 10 cm in diameter. Using a photolithography process, the pattern is replicated on the top surface of the wafer, and the process is well known. The wafer is coated with a photoresist on its upper surface and then exposed to UV light irradiation through a mask member having transparent and opaque regions corresponding to the pattern. After development of the resist, the resist portion remaining on the wafer replicates the pattern and has a replication accuracy of up to 0.02 μm.

  Also, as long as the remaining resist portion has a well-defined thickness and is sufficiently robust not to deteriorate during stamp molding, the wafer may be used as a master 11 with the remaining resist portion. it can. Alternatively, the wafer is etched using a known process such as plasma etching or wet etching. The resist is then completely removed and the wafer is placed on the base 10 for use as the master 11. As a result, a pattern is formed on the upper surface of the mold bottom 1 and appears. A further low energy surface coating or anti-sticking layer is preferably applied on the wafer.

  FIG. 2 is a cross-sectional view of the mold 100 during assembly along the line II-II shown in FIG. The lower mold side portion 12 has a cylindrical first bore having an inner diameter D of 10 mm to 100 mm. The height h of the first bore is, for example, 1.0 mm to 5.0 mm. The upper mold side portion 13 has a cylindrical second bore, and its inner diameter is D + 2Δ. Here, the Δ value is between 1 mm and 10 mm. The pattern is indicated by P. The pattern exists on the upper surface of the master 11 in a circle having a diameter D.

  After the mold 100 is assembled, a first liquid elastomer is injected into the mold, resulting in the formation of a continuous liquid layer A on the master 11 in the first bore. The mold 100 is rotated about its axis during the injection of the first elastomer to form an elastomer layer having a uniform thickness. The first elastomer is dried in the mold 100. Since the bottom surface of the layer A is mutually opposite to the top surface of the master 11, the pattern P is replicated on the bottom surface of the layer A. The amount of the injected first elastomer is adjusted so that the thickness of the layer A is 50 μm to 500 μm at least in the region corresponding to the pattern, and then the first elastomer is partially solidified. A second liquid elastomer is injected into the mold 100, resulting in the formation of another layer, designated B, over the layer A. The mold can also be rotated. The second elastomer hardens, for example so that the two layers adhere to each other. The amount of injected second elastomer is adjusted so that the upper surface of layer B is higher than the upper edge of the first bore. That is, layer A and layer B have a total thickness e, which is greater than the value of the first bore height h. Usually, the total thickness of the layer A and the layer B is selected to be 1 mm to 10 mm.

  Layer A and layer B form the elastic diaphragm of the stamp, and the bottom surface of layer A forms the stamp surface. The elastomer of layer A is selected to be harder than the elastomer of layer B, so that the pattern P replicated on the stamp surface is a machine that is being stamped, even if the pattern P is very fine It only suffers from minimal deformation. Layer B serves as the soft backplane for layer A. Thus, the diaphragm can be deformed to conform to the curvature of the receiving surface during the stamping operation.

  The elastomer of layer B may be a siloxane type. For example, a commercial product supplied by Dow Corning under the name Sylgard (registered trademark) 184 may be used. The Young's modulus of layer B is between 0.5 MPa and 2.5 MPa, corresponding to a fairly soft material. The cure status of Sylgard (R) 184 is indicated by the supplier.

  The elastomer of layer A may also be a siloxane type and is modified to have a Young's modulus of 5 MPa to 15 MPa.

  In another embodiment of the present invention, the siloxane type elastomers of layer A and layer B can transmit UV light (ultraviolet light). For example, Sylgard (R) 184 meets this requirement by exhibiting moderate absorption at wavelengths between 250 nm and 400 nm (nanometers).

  It is also possible to inject a second elastomer into the mold 100 immediately after injecting the first elastomer and to dry both layer A and layer B simultaneously. It has been observed that drying at 60 ° C. for several hours to several days is appropriate.

  When the method of manufacturing a stamp further includes the step of applying a second elastomer adhesion promoter to the inner surface of the upper mold side portion 13, it is used to fix the pressing during printing and / or the pressing during printing. The assembly of the diaphragm using the rigid part to be performed is greatly simplified. This adhesion promoter is also called a primer. The primer must be applied to the upper mold side portion 13 before the elastomer is injected. The upper mold side portion 13 is used for stamping and / or fixing. For the embodiment of the present invention illustrated in FIGS. 1 and 2, an adhesion promoter is applied to the bore surface of the upper mold side portion 13. For example, an adhesion promoter supplied by Dow Corning Company, referred to as reference primer 92-023, can be used.

  Advantageously, the mold side part (in this example the mold part 13) having the largest bore has an edge with an inner groove on which an adhesion promoter is applied. The groove is shown as reference numeral 13a in FIG. Thus, by using the accelerator applicator and wiping the groove 13a, the adhesion promoter can be easily applied in the bore of the upper mold side portion 13 before the mold 100 is assembled.

  FIG. 3 shows the diaphragm 20 manufactured as described above. The diaphragm 20 is attached to the mold part 13 indicated by a broken line. The fixed surface of the diaphragm 20 includes an inclined peripheral edge corresponding to the groove 13a. Reference numeral 21 denotes a stamp surface on which a pattern P is formed. The stamp surface 21 is surrounded by a thinned elastomer ring 22. As an example, the diaphragm 20 has a disk shape having a diameter of 10 mm or more, preferably 70 mm. The diaphragm thickness in the stamp surface region is 1 mm or more, for example 3 mm, and the diaphragm thickness in the ring region is between 0.5 mm and 2.0 mm. The difference in diaphragm thickness between the stamp surface area and the ring area corresponds to the bore height h of the lower mold side portion 12. Obviously, the geometry parameter and the combination of geometry parameters for the mold 100 match the specific Young's modulus values of material A and material B.

  With reference to FIGS. 4a to 4c, the manufacturing process of an object having a pattern printed on a receiving surface with a pseudo-spherical surface is described. The receiving surface of the object has a radius of curvature greater than 10 mm. For example, the object is an ophthalmic lens having a convex or concave curvature radius of 50 mm to 200 mm and a diameter of 55 mm to 80 mm. The lens may be any material including organic materials such as polyethylene or acrylic acid based materials.

  The ink solution is selectively deposited using a stamp. The surface of the lens to be printed is first coated with a layer that exhibits chemical affinity for the ink, such as chemisorption. The layer may be conductive. Without limitation, the conductive layer can be a layer of metal selected from gold, silver, palladium, platinum, aluminum, and copper. The conductive layer may also be a doped oxide, such as indium tin oxide. The material of the conductive layer is selected so that it can be etched later. Known processes such as vapor deposition or sputtering can be used to deposit the conductive layer.

The stamp is then used to print a pattern on the conductive layer using ink formulated to protect the conductive layer from etching. The upper surface of the conductive layer forms a receiving surface of the lens used in the stamping process. Preferably, the ink is formulated to form a self-assembled monolayer on the conductive layer. The ink is very effective in protecting the conductive layer against etching because the deposited ink layer is very dense. The ink includes molecules having functional groups that bind to the conductive material. The remaining portion of each molecule (eg, long chain hydrocarbon) interacts with adjacent molecules to form a dense structure that is impermeable to the etchant. For example, hexadecanethiol (C ₁₆ H ₃₄ S) -based ink provided by Sigma Aldrich is compatible with a gold layer deposited on the lens receiving surface.

  The ink is transferred onto the stamp surface by any known method including direct inking, immersion in an ink tank, and ink spray. Excess ink on the stamp surface 21 is removed by blowing filtered air or nitrogen against the stamp surface.

  The stamp surface 21 is then pressed against the receiving surface of the lens, and the ink is deposited at a position corresponding to the pattern on the conductive layer. 4a to 4c, the reference symbol D indicates the direction of movement of the stamp relative to the receiving surface. Reference numeral 101 denotes a lens, reference numeral 102 denotes a conductive layer, and reference numeral 103 denotes a receiving surface.

  A vertical movement device is used to control the parameters of contact between the stamp surface 21 and the receiving surface 103. For example, if the receiving surface is a convex surface having a radius of curvature of 55 mm and the diaphragm 20 has the above-described region, the stamp is pressed at a speed of 10 cm / s, a maximum pressing force of 30 N, and an average contact time of 5 seconds. Is a suitable parameter to achieve a 65 mm diameter contact area.

  FIG. 4 a shows the situation when the stamp surface 21 of the diaphragm 20 starts to contact the receiving surface 103 of the lens 101. At this time, the diaphragm is not curved and contact occurs at a single point located on the axis of the lens. When the rigid body portion 13 is pushed down along the direction D, the diaphragm 20 is pushed up by the receiving side surface 103. The diaphragm 20 is distorted to an intermediate position so as to match the curvature of the lens 101 (FIG. 4b). In this way, the contact area between the stamp surface 21 and the receiving surface 103 gradually widens, thus avoiding bubble entrainment. The peripheral ring 22 continues to curve. Next, when the rigid body portion 13 is further pushed, the diaphragm 20 is distorted to the entire stamping region 21, and the ring 22 is further curved (FIG. 4c). In fact, since the vicinity of the periphery of the diaphragm 20 is thin, most of the curvature of the diaphragm 20 is concentrated on the ring 22. Therefore, the pattern P on the stamp surface 21 is slightly distorted. While the stamp surface 21 is being pressed by the receiving surface 103, the curvature of the stamp surface 21 may be optically monitored as required.

  FIGS. 5 a and 5 b show an embodiment of the present invention where the stamp further comprises a sealed housing 104 bounded by the diaphragm 20. The housing 104 is formed by matching the cap 14 above the rigid body portion 13. The shape of the stamp surface 21 can be controlled by the air pressure in the housing 104 using the opening 15. In contrast to the lens 101 having a convex receiving surface 103, the stamp surface 21 is concave in the previous stage and its absolute radius of curvature is larger than the absolute radius of curvature of the receiving surface 103 (FIG. 5a). This is obtained by using the opening 15 to reduce the air pressure in the housing 104. Thus, the diaphragm 20 is initially already curved, reducing the residual distortion of the stamp surface 21 that occurs when the stamp is pushed down against the receiving surface 103. By reducing the residual distortion on the stamp surface 21, the quality of the pattern printed on the receiving surface is improved. This is due to the fact that the distortion of the stamp surface 21 is more evenly distributed by pneumatic control and that the sliding of the diaphragm 20 on the receiving surface 103 hardly occurs during the stamping operation. If desired, the cap 14 has a smaller bore 16 that can adjust the pressure differential during stamping.

  If the receiving surface 103 is concave (FIG. 5b), the stamp surface 21 is initially convex and has an absolute radius of curvature that is smaller than the absolute radius of curvature of the receiving surface. This is achieved by using the opening 15 to increase the air pressure within the housing 104. When this pressure is higher than the pressure outside the housing 104, the stamp surface is convex. Then, when the stamp is depressed along direction D, the stamp surface 21 penetrates deeply into the receiver surface 103 so that the first contact occurs at the center point of the stamp surface. If desired, the cap 14 has another small bore 16 that can adjust the pressure differential during stamping.

After removing the stamp from the object, the receiving surface 103 of the lens 101 comes into contact with the etchant so that the conductive layer 102 is etched at a point on the receiving surface where no ink is deposited during the stamping operation. . A process known as wet etching can be used depending on the material of the conductive layer. In particular, a solution containing 40 mmol / liter iron nitrate (Fe (NO ₃ ) ₃ ) and 60 mmol / liter thiourea (CH ₄ N ₂ S) is suitable for etching the gold layer at ambient temperature. Yes. A pH-adjusted cyanide solution can also be used as the etching solution. After etching, the conductive layer 102 remains according to the pattern P only at the points coated with the ink deposited by the stamp.

  6a and 6b show an example of a pattern P printed on the receiving surface 103 of the lens 101. FIG. 6b is a cross-sectional view of the lens 101 according to the arrow VIb shown in FIG. 6a. The pattern P is a linear conductive grid and is composed of a set of parallel conductive lines 110. Each line corresponds to the rest of the conductive layer 102. Advantageously, the grid has a spacing p in the range of 0.1 μm to 0.4 μm, preferably in the range of 0.14 μm to 0.25 μm. And, the visible light impinging on the lens 101 is not diffracted, so that the lens meets the aesthetic requirements of an ophthalmic lens. The grid causes a partial polarization effect on the light striking the optical lens. In known methods, the polarization action is useful for reducing glare caused by the reflection plane. Other features of the grid are: a grid line made of silver or aluminum, depending on the material of the layer 102 and a line thickness t of 30 nm (nanometers) or more depending on the thickness of the layer 102 and the stamp surface 21 A line width of 0.15 μm or less specified by the pattern P replicated above and within a range of 16% to 95% with respect to a polarization component orthogonal to the grid line, and to a polarization component parallel to the grid line On the other hand, it can be the visible transmission of the lens within a range of 0% to 5%.

  It is clear that the polarizing linear grid geometry parameters are adapted to the specific properties of the conductive layer 102. This pattern example is given for illustrative purposes only. Other patterns can be printed on the lens using functions other than polarization. Using the manufacturing method of the present invention, the inventors also typically manufactured lenses using infrared light with a wavelength of 1.3 μm or 1.5 μm.

  Further, it will be apparent that the invention described in detail can be adapted or modified to suit a particular application and various embodiments of soft lithography. For example, the pattern can be printed positively or negatively in a way that can be derived directly from the described implementation. In particular, it is easy to use the present invention to implement a technique called “Positive Microcontact Printing”. This example is described in Non-Patent Document 3. The present invention is also useful for implementing the “Electroless deposition” technique by using specific catalyst molecules as ink on the stamp. This example is described in Non-Patent Document 4. The present invention may also be useful for implementing micromold techniques such as UV embossing or hot embossing. Some examples are described in Non-Patent Document 1. In the particular case of UV embossing, the elastomeric material of the stamp needs to be transparent to UV light.

  In another embodiment, the present invention provides a method of manufacturing an object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101), Applying a polymerizable liquid to the receiving surface, using a stamp containing a siloxane-type elastomer that transmits UV light, and pressing the stamp surface (21) against the receiving surface (103) of the object And curing the liquid with UV light and removing the stamp from the object.

  In a similar manner, the object of the present invention is to provide a method for producing an object having a pattern (P) printed on a receiving surface (103) in the form of a pseudo-spherical surface of the object (101). A step of applying a polymerizable liquid to the surface, a step of using a stamp containing a siloxane-type elastomer that transmits UV light, and a step of pressing the stamp surface (21) against the receiving surface (103) of the object. And curing the liquid with UV light and removing the stamp from the object.

  It is clear that in both molding methods cited above, it is also feasible to heat cure the polymerizable liquid.

1 is a perspective view of a mold for manufacturing a stamp according to the present invention. FIG. It is sectional drawing of the mold of FIG. It is a perspective view of the stamp manufactured by using the mold of FIG. The process of printing a pattern on the ophthalmic lens of this invention is shown. The process of printing a pattern on the ophthalmic lens of this invention is shown. The process of printing a pattern on the ophthalmic lens of this invention is shown. Two implementations of the printing process on a convex receiving surface and a concave receiving surface are shown. Two implementations of the printing process on a convex receiving surface and a concave receiving surface are shown. FIG. 2 is a plan view and a cross-sectional view of an ophthalmic lens having a pattern printed according to the present invention. FIG. 2 is a plan view and a cross-sectional view of an ophthalmic lens having a pattern printed according to the present invention.

Claims (37)

  A stamp for patterning on the receiving side in accordance with a designated pattern (P), comprising a stamp surface (21) of an elastic diaphragm (20) that is flat in a stationary state and on which the pattern is duplicated, the diaphragm The diaphragm moves to the rigid body portion (13) along the peripheral edge of the diaphragm so that the middle point of the diaphragm is movable relative to the rigid body portion along a direction perpendicular to the stamp surface (21). The stamp is attached, the stamp being characterized in that the diaphragm is more elastic in the vicinity of the peripheral portion than in the intermediate portion.   The stamp according to claim 1, wherein the diaphragm (20) is thinner in the ring-shaped part near the peripheral edge than in an intermediate part surrounded by the ring-shaped part (22).   The diaphragm (20) includes a plurality of elastic layers (A, B) stacked in a direction perpendicular to the stamp surface (21), and the stamp surface has the highest hardness among the layers of the diaphragm. The stamp of Claim 1 or 2 containing the said elastic layer (A) which has.   4. The stamp according to claim 3, wherein the elastic layer (A) having the highest hardness has a thickness between 50 [mu] m and 500 [mu] m in at least one region of the stamp surface corresponding to the pattern (P).   The sealed housing (104) bounded by the diaphragm (20) and the pressure in the housing is varied to control the concave or convex surface of the stamp surface (21) by the pressure. The stamp according to any one of claims 1 to 4, further comprising means for enabling.   The stamp according to any one of claims 1 to 5, wherein at least a part of the elastic diaphragm is formed from a siloxane-type elastomer.   The stamp according to claim 6, wherein the siloxane-type elastomer transmits ultraviolet light.   The diaphragm (20) has a diameter of 10 mm or more, a thickness of 2.5 mm or more in the stamp surface area of the diaphragm, and a thickness of 0.5 to 2.0 mm in the ring-shaped portion (22). The stamp according to any one of claims 2 to 7, which has a disc shape.   The stamp according to claim 8, wherein the ring-shaped part of the diaphragm (20) has a difference between 1 mm and 10 mm between a long diameter and a short diameter. Providing the mold bottom (1) with a pattern (P) replicated on a plane of the mold bottom;
Disposing the mold side portion (2) on the mold bottom portion (1) such that an inner bottom end of the mold side portion surrounds the pattern (P), the mold side portion (2) Comprises a lower mold side part (12) and an upper mold side part (13), the individual internal bores are arranged in a line, and one of the mold side parts is connected to the other mold side part. A process made larger in cross-section than bore,
The mold bottom (1) and the mold side overlaid to form an elastomer diaphragm (20) having a thickness (e) that is higher than the height (h) of the bore in the lower mold side portion (12). Injecting at least one elastomer precursor into said mold (100) comprising part (2);
Fixing the diaphragm to a rigid body portion (13) along a peripheral edge portion of the diaphragm (20) corresponding to the largest bore of the lower mold side portion and the upper mold side portion. Production method.   The stamp manufacturing method according to claim 10, wherein the pattern (P) is formed on an upper surface of the mold bottom (1).   The stamp manufacturing method according to claim 10 or 11, wherein a bore of the upper mold side part (13) is larger than a bore of the lower mold side part (12).   Before injecting the elastomer precursor, applying an adhesion promoter for the elastomer to the inner surface of the mold side portion having the largest bore, the mold side portion having the largest bore being The stamp manufacturing method according to any one of claims 10 to 12, further comprising a step of being a part of the rigid portion (13).   The stamp manufacturing method according to claim 13, wherein the mold side portion having the largest bore (13) comprises an inner groove (13a) to which the adhesion promoter is applied.   The lower mold side part (12) and the upper mold side part (13) are separate parts, and means are provided for joining the lower mold side part and the upper mold side part in a row. Item 15. The stamp manufacturing method according to any one of Items 10 to 14. A method of manufacturing the object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101),
Applying ink to the stamp surface (21) of the stamp according to any one of claims 1 to 6, or 8, or 9;
Pressing the stamp surface (21) of the stamp against the receiving surface (103) of the object;
Removing the stamp from the object;
Processing the receiving surface by wet etching or chemical plating. A method of manufacturing the object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101),
A step of laminating a light absorbing layer on the concave stamp surface;
Applying a photoresist to the receiving surface;
The stamp according to any one of claims 1 to 5 or 7 to 9 as a light coupling mask by pressing the stamp surface (21) against the receiving surface (103) of the object. A step of exposing the stamp to ultraviolet light; and
Removing the stamp from the object;
Developing the photoresist.   18. A method for manufacturing an object according to claim 16 or 17, wherein the receiving surface has a radius of curvature greater than 55 mm and is concave or convex. Before pressing the stamp surface (21) of the stamp against the receiving surface (103) of the object,
The stamp surface (21) and the receiver surface (103) have complementary shapes, and pressing the stamp surface against the receiver surface starts by contacting at an intermediate portion of the stamp surface The method of manufacturing an object according to any one of claims 5 or 16 to 18, further comprising adjusting the pressure in the housing (104) as described.   20. The object according to any one of claims 16 to 19, wherein the curvature of the stamp surface is optically monitored while pressing the stamp surface (21) against the receiving surface (103). How to manufacture.   The method of manufacturing an object according to claim 16, wherein the ink is formulated to form a self-assembled monolayer on the conductive layer (102).   The method for producing an object according to claim 16, wherein the ink is a solution of catalyst molecules.   The method of manufacturing an object according to claim 21, wherein the conductive layer (102) is a metal layer.   24. A method of manufacturing an object according to claim 23, wherein the metal is selected from gold, silver, palladium, platinum, aluminum, and copper.   25. A method for manufacturing an object according to any one of claims 16 to 24, wherein the object comprises an optical lens (101).   26. A method for manufacturing an object according to claim 25, wherein the optical lens (101) is an ophthalmic lens.   27. A method for manufacturing an object according to claim 25 or 26, wherein the pattern (P) comprises a linear conductive grid.   28. A method of manufacturing an object according to claim 27, wherein the grid has a spacing (p) in the range of 0.1 [mu] m to 0.4 [mu] m.   29. A method of manufacturing an object according to claim 28, wherein the grid spacing (p) is in the range of 0.14 [mu] m to 0.25 [mu] m.   30. A method of manufacturing an object according to any one of claims 27 to 29, wherein the grid includes parallel conductive lines (110) having a thickness (t) of 30 nm or more.   31. A method for manufacturing an object according to any one of claims 27 to 30, wherein the width (l) of the grid lines (110) is 0.15 [mu] m or less.   32. A method according to any one of claims 27 to 31, wherein the grid produces at least a partial polarization effect on light impinging on the optical lens (101).   The transmittance of the lens in the visible light region is in the range of 16% to 95% with respect to the polarization component orthogonal to the grid line (110), and with respect to the polarization component parallel to the grid line. 35. The method of claim 32, wherein the method is in the range of 0% to 5%. A method of manufacturing the object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101),
Applying a polymerizable liquid to the receiving surface;
Using the stamp of claim 7;
Pressing the stamp surface (21) against the receiving surface (103) of the object, curing the liquid with ultraviolet light; and
Removing the stamp from the object. A method of manufacturing the object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101),
Applying a polymerizable liquid to the stamp surface;
Using the stamp of claim 7, and pressing the stamp surface (21) against the receiving surface (103) of the object, curing the liquid with ultraviolet light; and
Removing the stamp from the object. A method of manufacturing the object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101),
Applying a polymerizable liquid to the receiving surface;
Using the stamp according to any one of claims 1 to 6;
Pressing the stamp surface (21) against the receiving surface (103) of the object, curing the liquid by thermosetting;
Removing the stamp from the object. A method of manufacturing the object having a pattern (P) printed on a receiving surface (103) having a pseudo-spherical shape of the object (101),
Applying a polymerizable liquid to the stamp surface;
Using the stamp according to any one of claims 1 to 6;
Pressing the stamp surface (21) against the receiving surface (103) of the object, curing the liquid by thermosetting;
Removing the stamp from the object.

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